Spheroidal titanium metallic powders with custom microstructures

ABSTRACT

Methodologies, systems, and devices are provided for producing metal spheroidal powder products. By utilizing a microwave plasma, control over spheriodization and resulting microstructure can be tailored to meet desired demands.

RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/012,370, filed Jun. 19, 2018 (US Patent Publication No.2018/0297122), which is a continuation in part of U.S. patentapplication Ser. No. 15/381,336 (US Patent Publication No. US2017/0173699), which claims priority to and the benefit of U.S.Provisional Patent Application No. 62/268,186, filed Dec. 16, 2015. Eachof the foregoing applications is incorporated herein by reference in itsentirety.

TECHNICAL FIELD

The present disclosure is generally directed towards producing metalspheroidal powder products. More particularly, the present disclosure isdirected towards techniques for producing metal spheroidal powderproducts (e.g., Ti powders, Ti alloy powders, Ti compound powders) usinga microwave generated plasma.

BACKGROUND

An important aspect of preparing some forms of industrial powders is thespheroidization process, which transforms irregularly shaped or angularpowders produced by conventional crushing methods, into sphericallow-porosity particles. Spherical powders are homogenous in shape,denser, less porous, have a high and consistent flowability, and hightap density. Such powders exhibit superior properties in applicationssuch as injection molding, thermal spray coatings, additivemanufacturing, etc.

Creating spheroidal metallic powders, especially metallic powderscontaining Ti, can pose a number of challenges. Achieving the desiredspheroidal shape, the desired level of porosity (e.g., no porosity tovery porous, and the desired composition and microstructure can bedifficult.

Conventional spheroidization methods employ thermal arc plasma describedin U.S. Pat. No. 4,076,640 issued Feb. 28, 1978 and radio-frequencygenerated plasma described in U.S. Pat. No. 6,919,527 issued Jul. 19,2005. However, these two methods present limitations inherent to thethermal non-uniformity of radio-frequency and thermal arc plasmas.

In the case of thermal arc plasma, an electric arc is produced betweentwo electrodes generates a plasma within a plasma channel. The plasma isblown out of the plasma channel using plasma gas. Powder is injectedfrom the side, either perpendicularly or at an angle, into the plasmaplume, where it is melted by the high temperature of the plasma. Surfacetension of the melt pulls it into a spherical shape, then it is cooled,solidified and is collected in filters. An issue with thermal arc plasmais that the electrodes used to ignite the plasma are exposed to the hightemperature causing degradation of the electrodes, which contaminatesthe plasma plume and process material. In addition, thermal arc plasmaplume inherently exhibit large temperature gradient. By injecting powderinto the plasma plume from the side, not all powder particles areexposed to the same process temperature, resulting in a powder that ispartially spheroidized, non-uniform, with non-homogeneous porosity.

In the case of radio-frequency inductively coupled plasmaspheroidization, the plasma is produced by a varying magnetic field thatinduces an electric field in the plasma gas, which in turn drives theplasma processes such as ionization, excitation, etc. . . . to sustainthe plasma in cylindrical dielectric tube. Inductively coupled plasmasare known to have low coupling efficiency of the radio frequency energyinto the plasma and a lower plasma temperature compared to arc andmicrowave generated plasmas. The magnetic field responsible forgenerating the plasma exhibits a non-uniform profile, which leads to aplasma with a large temperature gradient, where the plasma takes adonut-like shape that exhibiting the highest temperature at the edge ofthe plasma (close to the dielectric tube walls) and the lowesttemperature in the center of the donut. In addition, there is acapacitive component created between the plasma and the radio frequencycoils that are wrapped around the dielectric tube due to the RF voltageon the coils. This capacitive component creates a large electric fieldthat drives ions from the plasma towards the dielectric inner walls,which in turn leads to arcing and dielectric tube degradation andprocess material contamination by the tube's material.

To be useful in additive manufacturing or powdered metallurgy (PM)applications that require high powder flow, metal powder particlesshould exhibit a spherical shape, which can be achieved through theprocess of spheroidization. This process involves the melting ofparticles in a hot environment whereby surface tension of the liquidmetal shapes each particle into a spherical geometry, followed bycooling and re-solidification. Also, spherical powders can be directlyproduced by various techniques. In one such technique, a plasma rotatingelectrode (PRP) produces high flowing and packing titanium and titaniumalloy powders but is deemed too expensive. Also, spheroidized titaniumand titanium alloys have been produced using gas atomization, which usesa relatively complicated set up an may introduce porosity to the powder.Spheroidization methods of irregular shape powders include TEKNA's(Sherbrook, Quebec, Canada) spheroidization process using inductivelycoupled plasma (ICP), where angular powder obtained fromHydride-Dehydride (HDH) process is entrained within a gas and injectedthough a hot plasma environment to melt the powder particles. However,this method suffers from non uniformity of the plasma, which leads toincomplete spheroidization of feedstock. The HDH process involvesseveral complex steps, including hydrogenation dehydrogenation, anddeoxidation before the powder is submitted to spheroidization. Thisprocess is a time consuming multi-step process, which drives up the costof metal powders made through these methods.

From the discussion above, it is therefore seen that there exists a needin the art to overcome the deficiencies and limitations described hereinand above.

SUMMARY

The shortcomings of the prior art are overcome and additional advantagesare provided through the use of a microwave generated plasma torch andselecting and controlling cooling processing parameters to generatespheroidized metallic particles with a desired microstructure. Exemplaryembodiments of the present technology are directed to spheroidaltitanium (e.g., titanium and titanium alloy) particles and methods forpreparing such particles.

In one aspect, the present disclosure relates to spheroidized particlesincluding titanium. The spheroidized particles are prepared by a processincluding: introducing a titanium based feed material (e.g., feedmaterial includes titanium, such as titanium particles or titanium alloypowders) including particles into a microwave plasma torch; melting andspheroidizing the feed material within a plasma generated by themicrowave plasma torch; exposing the spheroidized particles to an inertgas; and setting one or more cooling processing variables to tailor themicrostructure of the spheroidized particles including titanium. Theabove aspect includes one or more of the following features. In oneembodiment, the titanium based feed material includes a titanium alloy.In another embodiment, the spheroidized particles are Ti Al6-V4 (i.e.,Ti 6-4). In another embodiment, melting and spheroidizing of the feedmaterial occurs within a substantially uniform temperature profilebetween about 4,000K and 8,000K. In another embodiment, the feedmaterial has a particle size of no less than 1.0 micrometers and no morethan 300 micrometers. In another embodiment, one or more coolingprocessing variables are set to create a martensitic microstructure inthe spheroidized particles. In another embodiment, one or more coolingprocessing variables are set to create a Widmanstätten microstructure inthe spheroidized particles. In another embodiment, one or more coolingprocessing variables are set to create an equiaxed microstructure in thespheroidized particles. In another embodiment, one or more coolingprocessing variables are set to create at least two regions, each regionhaving a different microstructure. In another embodiment, the at leasttwo regions include a core portion and a skin portion. In anotherembodiment, the skin portion has a microstructure that is different fromthe feed material's microstructure.

In another aspect, the present disclosure relates to a method oftailoring microstructure of spheroidized metallic particles. The methodincludes introducing a metal feed material including particles into amicrowave plasma torch. The method also includes melting andspheroidizing the feed material within a plasma generated by themicrowave plasma torch; exposing the spheroidized particles to an inertgas; and setting one or more cooling processing variables to tailor themicrostructure of the spheroidized metallic particles. The above aspectincludes one or more of the following features. In one embodiment, themetal feed material includes a titanium based feed material. In anotherembodiment, melting and spheroidizing of the feed material occurs withina substantially uniform temperature profile between about 4,000K and8,000K. In another embodiment, the feed material has a particle size ofno less than 1.0 micrometers and no more than 300 micrometers. Inanother embodiment, setting one or more cooling processing variablesincludes selecting and controlling a cooling gas flow rate. In anotherembodiment, setting one or more cooling processing variables includesselecting and controlling a residence time of the particles of feedmaterials within the plasma. In another embodiment, setting one or morecooling processing variables includes selecting and controlling acooling gas composition. In another embodiment, the cooling gascomposition is selected to provide high thermal conductivity. In anotherembodiment, one or more cooling processing variables are set to create amartensitic microstructure in the spheroidized particles. In anotherembodiment, one or more cooling processing variables are set to create aWidmanstätten microstructure in the spheroidized particles. In anotherembodiment, one or more cooling processing variables are set to createan equiaxed microstructure in the spheroidized particles. In anotherembodiment, one or more cooling processing variables are set to createat least two regions, each region having a different microstructure. Inanother embodiment, the at least two regions include a core portion anda skin portion. In another embodiment, the skin portion has amicrostructure that is different from the feed material'smicrostructure.

In another aspect, the present disclosure relates to a method ofmodifying at least one of particle shape or microstructure of a titaniumbased feed stock. The method includes selecting a composition of thetitanium based metal feed stock; determining a desired microstructurefor a final product; selecting cooling process parameters based upondesired microstructure and composition of the titanium based metal feedstock; melting at least a surface portion of particles of the titaniumbased metal feed stock in a plasma having a substantially uniformtemperature profile at between 4,000K and 8,000K to spheriodize the feedstock; exposing the spheroidized particles to an inert gas; and settingand applying the selected cooling processing parameters to createspheroidized particles with the desired microstructure. The above aspectincludes one or more of the following features. In one embodiment,selecting the composition of the titanium based metal feed materialincludes determining an alloying composition of a titanium based feedstock source. In another embodiment, the particles of the titanium basedmetal feed stock have a particle size of no less than 1.0 micrometersand no more than 300 micrometers. In another embodiment, setting andapplying the selected cooling processing parameters includes controllinga cooling gas flow rate. In another embodiment, setting and applying theselected cooling processing parameters include controlling a residencetime of the particles of the titanium based metal feed stock in theplasma. In another embodiment, setting and applying the selected coolingprocessing parameters includes controlling a cooling gas composition. Inanother embodiment, the cooling gas composition is selected to providehigh thermal conductivity. In another embodiment, the cooling processingparameters are selected to create a martensitic microstructure in thespheroidized particles. In another embodiment, the cooling processingparameters are selected to create a Widmanstätten microstructure in thespheroidized particles. In another embodiment, the cooling processingparameters are selected to create an equiaxed microstructure in thespheroidized particles. In another embodiment, the cooling processingparameters are selected to create at least two regions, each regionhaving a different microstructure or crystal structure. The at least tworegions can include a core portion and a skin portion. In anotherembodiment, the skin portion has a microstructure that is different fromthe feed stock's microstructure. In another embodiment, the titaniumbased metal feed stock has a α-phase crystal structure and thespheroidized particles includes one or more regions of a β-phase crystalstructure. In another embodiment, the titanium based metal feed stockhas a single phase structure and the spheroidized particles have amultiphase structure.

Embodiments of the above aspects may include one or more of thefollowing features. The various spheroidized particles, processes usedto create the spheroidized particles, and methods of producing metal ormetal alloy powders in accordance with the present technology canprovide a number of advantages. For example, the particles, processesfor forming the particles and methods disclosed herein can be used in acontinuous process that spheroidizes, and allows for control over thefinal microstructure of the particles. Such embodiments can reduce thecost of spheroidizing metal powders by reducing the number of processingsteps, which in turn, reduces the energy per unit volume of processedmaterial and can increase the consistency of the final product.Reduction in the number of processing steps also reduces the possibilityfor contamination by oxygen and other contaminants. Additionally, thecontinuous processes disclosed herein improve the consistency of the endproducts by reducing or eliminating variations associated with typicalbatch-based processing of particles. The present technology can achieveadditional improvements in consistency due to the homogeneity andcontrol of the energy source (i.e., plasma process). Specifically, ifthe plasma conditions are well controlled, particle agglomeration can bereduced, if not totally eliminated, thus leading to a better particlesize distribution (on the same scale as the original feed materials).

In addition to the advantage of consistent end product, the presentmethods and resulting powders have the advantage of control and theability to tailor the microstructure of the end product. While notwishing to be bound by theory, it is believed that the methods disclosedherein provide control over heating and cooling processing conditions.As a result, by controlling and, in some embodiments, monitoring, atleast one cooling processing variable (e.g., cooling gas flow rate,residence time in cooling gas, and composition of cooling gas) a desiredmicrostructure, which may be different from the original microstructurecan be obtained. Further, novel multiphase microstructures can becreated. That is, spheroidal particles can be processed by controllingheating and/or cooling conditions to create a core with onemicrostructure and a shell with a different microstructure. Someembodiments have the advantage of being able to modify or change themicrostructure of the feed stock material to a desired microstructure,which may be a single phase or multiphase material.

Additional features and advantages are realized through the techniquesof the present technology. The recitation herein of desirable objects oraspects which are met by various embodiments of the present technologyis not meant to imply or suggest that any or all of these objects oraspects are present as essential features, either individually orcollectively, in the most general embodiment of the present technologyor in any of its more specific embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

The features and advantages of the present disclosure will be more fullyunderstood from the following description of exemplary embodiments whenread together with the accompanying drawings, in which:

FIG. 1 illustrates an example method of producing spheroidal metallicand metallic alloy particles according to the present disclosure,compared against a conventional method for producing similar particles.

FIG. 2 illustrates another example method of producing dehydrogenatedspheroidal particles according to the present disclosure.

FIG. 3 illustrates another example method of producing dehydrogenatedspheroidal particles from metal hydride material according to thepresent disclosure.

FIG. 4 illustrates an exemplary microwave plasma torch that can be usedin the production of spheroidal and dehydrogenated metal or metal alloypowders, according to embodiments of the present disclosure.

FIG. 5 illustrates an exemplary method of producing titanium based(e.g., titanium, titanium alloy) spheroidal particles having a desiredmicrostructure.

FIG. 6 illustrates an exemplary method of modifying a particlemicrostructure according to embodiments of the present disclosure.

FIG. 7 illustrates an exemplary particle modified according toembodiments of the present disclosure.

DETAILED DESCRIPTION

One aspect of the present disclosure involves a process ofspheroidization of metals and metal alloy hydrides using a microwavegenerated plasma. The process uses readily available existingpre-screened or non-prescreened raw materials made of metal hydrides asfeedstock. The powder feedstock is entrained in inert and/or reducingand/or oxidizing gas environment and injected into the microwave plasmaenvironment. Upon injection into a hot plasma, the feedstock issimultaneously dehydrogenated and spheroidized and released into achamber filled with an inert gas and directed into hermetically sealeddrums where is it stored. This process can be carried out at atmosphericpressure, in a partial vacuum, or at a slightly higher pressure thanatmospheric pressure. In alternative embodiments, the process can becarried out in a low, medium, or high vacuum environment. The processcan run continuously and the drums are replaced as they fill up withspheroidized dehydrogenated and deoxidized metal or metal alloyparticles. The process not only spheroidizes the powders, but alsoeliminates the dehydrogenation steps from the traditional process ofmanufacturing metal and metal alloy powders using Hydride-De-hydride(HDH) process, which leads to cost reduction. By reducing the number ofprocessing steps and providing a continuous process, the possibilitiesfor contamination of the material by oxygen and other contaminants isreduced. Furthermore, provided the homogeneity of the microwave plasmaprocess, particle agglomeration is also reduced, if not totallyeliminated, thus leading to at least maintaining the particle sizedistribution of the original hydride feed materials.

In the powdered metallurgy industry, the Hydride-Dehydride (HDH) processis used to resize large metallic or metallic alloy pieces down to afiner particle size distribution through crushing, milling, andscreening. Metal and alloy powders are manufactured using the HDHprocess, where bulk feedstock, such as coarse metal powders ormetal/metal alloy scraps, etc., are heated in a hydrogen-containingatmosphere at high temperature (˜700° C.) for a few days. This leads tothe formation of a brittle metal hydride, which can readily be crushedinto a fine power and sifted to yield a desired size distributiondetermined by the end user. To be useful in powdered metallurgy,hydrogen must be dissociated and removed from the metal by heating themetal hydride powder within vacuum for a period of time. Thedehydrogenated powder must then be sifted to remove large particleagglomerations generated during process due to sintering. The typicalresulting powder particles have an irregular or angular shape. Thepowder is submitted to a deoxidation process to remove any oxygen pickedup by the powder during sifting and handling. Conventional HDH processesproduce only coarse and irregular shaped particles. Such HDH processesmust be followed by a spheroidization process to make these particlesspheroidal.

Conventional HDH processes are primarily carried out as solid-statebatch processes. Typically, a volume of metal powder is loaded into acrucible(s) within a vacuum furnace. The furnace is pumped down to apartial vacuum and is repeatedly purged with inert gas to eliminate thepresence of undesired oxygen. Diffusion of the inert gas through theopen space between the powder particles is slow making it difficult tofully eliminate oxygen, which otherwise contaminates the final product.Mechanical agitation may be used to churn powder allowing for morecomplete removal of oxygen. However, this increases the complexity ofthe system and the mechanical components require regular maintenance,ultimately increasing cost.

Following oxygen purging the, hydrogenation may begin. The furnace isfilled with hydrogen gas and heated up to a few days at high temperatureto fully form the metal hydride. The brittle nature of the metal hydrideallows the bulk material to be crushed into fine powders which are thenscreened into desired size distributions.

The next step is dehydrogenation. The screen hydride powder is loadedinto the vacuum furnace then heated under partial vacuum, promotingdissociation of hydrogen from the metal hydride to form H₂ gas anddehydrided metal. Dehydrogenation is rapid on the particle surface whereH₂ can readily leave the particles. However, within the bulk of thepowder, H₂ must diffuse through the bulk of the solid before it reachessurface and leave the particle. Diffusion through the bulk is arate-limiting process “bottle-neck” requiring relatively long reactiontime for complete dehydrogenation. The time and processing temperaturesrequired for dehydrogenation are sufficient to cause sintering betweenparticles, which results in the formation of large particleagglomerations in the final product. Post-process sifting eliminates theagglomerations, which adds process time and cost to the final product.Before the powder can be removed from the furnace, it must besufficiently cooled to maintain safety and limit contamination. Thethermal mass of the large furnaces may take many hours to sufficientlycool. The cooled powders must then be spheroidized in a separatemachine. Generally this is carried out within an RF plasma, which areknown to exhibit large temperature gradients resulting in partiallyspheroidized products.

Techniques are disclosed herein for manufacturing spheroidal metal andmetal alloy powder products in a continuous process that simultaneouslydehydrogenates and spheroidizes feed materials. According to exemplaryembodiments, the dehydrogenation and spheroidization steps of an HDHprocess can be simplified to a single processing step using a microwavegenerated plasma. Such embodiments can reduce the cost of spheroidizingmetal powders by reducing the number of processing steps, reducing theenergy per unit volume of processed material, and increasing theconsistency of the final product. Reduction in the number of processingsteps also reduces the possibility for powder contamination by oxygenand other contaminants. Additionally, the continuous dehydrogenationprocesses disclosed herein improves the consistency of the end productsby reducing or eliminating variations associated with typicalbatch-based dehydrogenation processes.

The rate of cooling of the dehydrogenated, deoxidized, and spheroidizedmetal and metal alloys can be controlled to strategically influence themicrostructure of the powder. For example, rapid cooling of α-phasetitanium alloys facilitates an acicular (martensite) structure. Moderatecooling rates produce a Widmanstätten microstructure, and slow coolingrates form an equiaxed microstructure. By controlling the processparameters such as cooling gas flow rate, residence time, cooling gascomposition etc., microstructure of the metal and metal alloys can becontrolled. In general, process parameters such as power density, flowrates, and residence time of the powder in the plasma dependent on thepowder material's physical characteristics, such as, for example, themelting point, thermal conductivity, and particle size distribution. Insome embodiments, the power density can range from about 20 W/cm³ to 500W/cm³. In certain embodiments, the total gas flow rate can range fromabout 0.1 cfm (cubic feet per minute) to 50 cfm. In embodiments, theresidence time can be tuned from about 1 milliseconds to 10 seconds. Theprecise cooling rates required to form these structures is largely afunction of the type and quantity of the alloying elements within thematerial.

The rate of cooling, especially when combined with the consistent anduniform heating capabilities of a microwave plasma plume, allow forcontrol over the final microstructure. As a result, the above methodscan be applied to processing metal (e.g., titanium and titanium alloyssuch as Ti 6-4) feed stock. In particular, while certain methods hereinhave described the use of a metal hydride feed stock, the control overmicrostructure is not limited thereto. In particular, methods of thepresent technology and powders created by the present technology includethe use of non-hydrided sources. For example, titanium metal and varioustitanium metal alloys can be utilized as the feed stock source. Thesematerials can be crushed or milled to create particles for treatmentwithin a microwave plasma torch.

Cooling processing parameters include, but are not limited to, coolinggas flow rate, residence time of the spheroidized particles in the hotzone, and the composition or make of the cooling gas. For example, thecooling rate or quenching rate of the particles can be increased byincreasing the rate of flow of the cooling gas. The faster the coolinggas is flowed past the spheroidized particles exiting the plasma, thehigher the quenching rate-thereby allowing certain desiredmicrostructures to be locked-in. Residence time of the particles withinthe hot zone of the plasma can also be adjusted to provide control overthe resulting microstructure. That is, the length of time the particlesare exposed to the plasma determines the extent of melting of theparticle (i.e., surface of the particle melted as compared to the innermost portion or core of the particle). Consequently, the extent ofmelting effects the extent of cooling needed for solidification and thusit is a cooling process parameter. Microstructural changes can beincorporated throughout the entire particle or just a portion thereofdepending upon the extent of particle melting. Residence time can beadjusted by adjusting such operating variables of particle injectionrate and flow rate (and conditions, such as laminar flow or turbulentflow) within the hot zone. Equipment changes can also be used to adjustresidence time. For example, residence time can be adjusted by changingthe cross-sectional area of the hot zone. For instance, for the same gasflow rates, a larger cross-sectional area of the plasma torch and/orextension tube in an afterglow region (e.g., region about plasma 11 inFIG. 4, the cross-sectional area being at least partially defined by theinner wall) will lead to a lower particle velocity, whereas a smallercross-sectional area will lead to a higher velocity, thus loweringresidence time in the hot zone.

Another cooling processing parameter that can be varied or controlled isthe composition of the cooling gas. Certain cooling gases are morethermally conductive than others. For example helium is considered to bea highly thermally conductive gas. The higher the thermal conductivityof the cooling gas, the faster the spheriodized particles can becooled/quenched. By controlling the composition of the cooling gas(e.g., controlling the quantity or ratio of high thermally conductivegasses, such as helium, to lesser thermally conductive gases, such asargon) the cooling rate can be controlled.

As is known in metallurgy, the microstructure of a metal is determinedby the composition of the metal and heating and cooling/quenching of thematerial. In the present technology, by selecting (or knowing) thecomposition of the feed stock material, and then exposing the feed stockto a plasm that has the uniform temperature profile and control thereover as provided by the microwave plasma torch, followed by selectingand controlling the cooling parameters control over the microstructureof the spheroidized metallic particle is achieved. In addition, thephase of the metallic material depends upon the compositions of the feedstock material (e.g., purity, composition of alloying elements, etc.) aswell thermal processing. Titanium has two distinct phases known as thealpha phase (which has a hexagonal close packed crystal structure) and abeta phase which has a body centered cubic structure. Titanium can alsohave a mixed α+β phase. The different crystal structures yield differentmechanical responses. Because titanium is allotropic it can be heattreated to yield specific contents of alpha and beta phases. The desiredmicrostructure is not only a description of the grains (e.g.,martensitic vs. equiaxed) but also the amount and location of differentphases throughout.

In one exemplary embodiment, inert gas is continually purged surroundinga powdered metal feed to remove oxygen within a powder-feed hopper. Acontinuous volume of powder feed is then entrained within an inert gasand fed into the microwave generated plasma for dehydrogenation or forcomposition/maintaining purity of the spheroidized particles. In oneexample, the microwave generated plasma may be generated using amicrowave plasma torch, as described in U.S. Patent Publication No. US2013/0270261, and/or U.S. Patent Publication No. US 2008/0173641 (issuedas U.S. Pat. No. 8,748,785), each of which is hereby incorporated byreference in its entirety. In some embodiments, the particles areexposed to a uniform temperature profile at between 4,000 and 8,000 Kwithin the microwave generated plasma. Within the plasma torch, thepowder particles are rapidly heated and melted. Liquid convectionaccelerates H₂ diffusion throughout the melted particle, continuouslybringing hydrogen (H₂) to the surface of the liquid metal hydride whereit leaves the particle, reducing the time each particle is required tobe within the process environment relative to bulk processes. As theparticles within the process are entrained within an inert gas, such asargon, generally contact between particles is minimal, greatly reducingthe occurrence of particle agglomeration. The need for post-processsifting is thus greatly reduced or eliminated, and the resultingparticle size distribution could be practically the same as the particlesize distribution of the input feed materials. In exemplary embodiments,the particle size distribution of the feed materials is maintained inthe end products.

Within the plasma, the melted metals are inherently spheroidized due toliquid surface tension. As the microwave generated plasma exhibits asubstantially uniform temperature profile, more than 90% spheroidizationof particles could be achieved (e.g., 91%, 93%, 95%, 97%, 99%, 100%),eliminating the need for separate dehydrogenation steps. In embodiments,which do not include dehydrogenation, both spheroidization and tailoring(e.g., changing, manipulating, controlling) microstructure are addressedor, in some instances, partially controlled, by treating with themicrowave generated plasma. After exiting the plasma, the particles arecooled before entering collection bins. When the collection bins fill,they can be removed and replaced with an empty bin as needed withoutstopping the process.

Embodiments of the present disclosure are directed to producingparticles that are substantially spherical or spheroidal or haveundergone significant spheroidization. In some embodiments, spherical,spheroidal or spheroidized particles refer to particles having asphericity greater than a certain threshold. Particle sphericity can becalculated by calculating the surface area of a sphere A_(s,ideal) witha volume matching that of the particle, V using the following equation:

$r_{ideal} = \sqrt{\frac{3V}{4\pi}}$ A_(s, ideal) = 4π r_(ideal)²

and then comparing that idealized surface area with the measured surfacearea of the particle, A_(s,actual):

${Sphericity} = \frac{A_{s,{ideal}}}{A_{s,{actual}}}$

In some embodiments, particles can have a sphericity of greater than0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 0.91, 0.95, or 0.99 (or greater thanabout 0.5, about 0.6, about 0.7, about 0.75, about 0.8, about 0.8, about0.91, about 0.95, or about 0.99). In some embodiments, particles canhave a sphericity of 0.75 or greater or 0.91 or greater (or about 0.75or greater or about 0.91 or greater). In some embodiments, particles canhave a sphericity of less than 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 0.91,0.95, or 0.99 (or less than about 0.5, about 0.6, about 0.7, about 0.75,about 0.8, about 0.8, about 0.91, about 0.95, or about 0.99). In someembodiments, a particle is considered to be spherical, spheroidal orspheroidized if it has a sphericity at or above any of theaforementioned sphericity values, and in some preferred embodiments, aparticle is considered to be spherical if its sphericity is at or about0.75 or greater or at or about 0.91 or greater.

In some embodiments, a median sphericity of all particles within a givenpowder can be greater than 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 0.91, 0.95, or0.99 (or greater than about 0.5, about 0.6, about 0.7, about 0.75, about0.8, about 0.8, about 0.91, about 0.95, or about 0.99). In someembodiments, a median sphericity of all particles within a given powdercan be less than 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 0.91, 0.95, or 0.99 (orless than about 0.5, about 0.6, about 0.7, about 0.75, about 0.8, about0.8, about 0.91, about 0.95, or about 0.99). In some embodiments, apowder is considered to be spheroidized if all or a threshold percentage(as described by any of the fractions below) of the particles measuredfor the given powder have a median sphericity greater than or equal toany of the aforementioned sphericity values, and in some preferredembodiments, a powder is considered to be spheroidized if all or athreshold percentage of the particles have a median sphericity at orabout 0.75 or greater or at or about 0.91 or greater.

In some embodiments, the fraction of particles within a powder that canbe above a given sphericity threshold, such as described above, can begreater than 50%, 60%, 70%, 80%, 90%, 95%, or 99% (or greater than about50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about99%). In some embodiments, the fraction of particles within a powderthat can be above a given sphericity threshold, such as described above,can be less than 50%, 60%, 70%, 80%, 90%, 95%, or 99% (or less thanabout 50%, about 60%, about 70%, about 80%, about 90%, about 95%, orabout 99%).

Particle size distribution and sphericity may be determined by anysuitable known technique such as by SEM, optical microscopy, dynamiclight scattering, laser diffraction, manual measurement of dimensionsusing an image analysis software, for example from about 15-30 measuresper image over at least three images of the same material section orsample, and any other techniques.

Referring to FIG. 1, shown is a comparison of a conventional process forproducing spheroidized titanium powder (100) versus a method (200) inaccordance with the present technology. The process flow (101) on theleft of FIG. 1 presents an example process that combines a HDH process(100) with spheroidization of titanium powders. The process starts withTi raw material (step a, 105) that is hydrogenated (step b, 110), andthen crushed and sifted to size (step c, 115). Pure titanium isrecovered through dehydrogenation (step d, 120). It is then screened foragglomerations and impurities, and then sifted to the size specified bythe customer (step e, 125). The powder then goes through a deoxidationstep to reduce or eliminate oxygen that it picked up during the siftingand screening processes. Deoxidation is required especially for smallparticle sizes, such as particles below 50 microns, where the surface tovolume ratio is substantial (step f, 130). The titanium particles arethen spheroidized (step g, 135) and collected (step h, 140). A similarprocess can be used to create a Ti alloy, such as Ti 6-4, instead ofpure titanium powder.

As discussed above, some embodiments of the present disclosure combinethe dehydrogenation and spheroidization steps shown on the left side ofFIG. 1 (101, 130, 135) in favor of a single step to produce spheroidizedmetals and/or metal alloys from corresponding hydride feedstock. Anexample of this technique is illustrated in the process flow (201) shownon the right side of FIG. 1. The method starts with a crushed and siftedmetal hydride feed material (i.e., step c, 115, without performing thedehydride step). In this particular embodiment, the feed material is atitanium hydride powder, and the powder resulting from process 200 is aspherical titanium powder. (It is noted that process 200 can also beused with crushed and sifted metal alloy hydride feed material, such astitanium alloy hydride feed material, and the powder resulting fromcompletion of process 200 is a spherical metal alloy powder, such as aspherical titanium alloy powder.) The powder is entrained within aninert gas and injected into a microwave generated plasma environmentexhibiting a substantially uniform temperature profile betweenapproximately 4,000 K and 8,000 K and under a partial vacuum. Thehermetically sealed chamber process can also run at atmospheric pressureor slightly above atmospheric pressure to eliminate any possibility foratmospheric oxygen to leak into the process. The particles aresimultaneously melted and dehydrogenated in the plasma, spheroidized dueto liquid surface tension, re-solidifying after exiting the plasma(200). The particles are then collected in sealed drums in an inertatmosphere (140). Within the plasma, the powder particles are heatedsufficiently to melt and cause convection of the liquid metal, causingdissociation of the hydrogen according to the reversible reaction whereM=an arbitrary metal:

$\left. {M_{x}H_{y}}\leftrightarrow{{(x)M} + {\left( \frac{y}{2} \right)H_{2}}} \right.$

Within the partial vacuum, dissociation of hydrogen from the metal toform hydrogen gas is favored, driving the above reaction to the right.The rate of dissociation of hydrogen from the liquid metal is rapid, dueto convection, which continually introduces H₂ to the liquid surfacewhere it can rapidly leave the particle.

FIG. 2 is a flow chart illustrating an exemplary method (250) forproducing spherical powders, according to an embodiment of the presentdisclosure. In this embodiment, the process (250) begins by introducinga feed material into a plasma torch (255). In some embodiments, theplasma torch is a microwave generated plasma torch or an RF plasmatorch. Within the plasma torch, the feed materials are exposed to aplasma causing the materials to melt, as described above (260). Duringthe same time (i.e., time that feed material is exposed to plasma),hydrogen within the feed material dissociates from the metal, resultingin dehydrogenation (260 a). Simultaneously the melted materials arespheroidized by surface tension, as discussed above (260 b). Note thatthe step 260 includes 260 a and 260 b. That is, by exposing the feedmaterial to the plasma both dehydrogenation and spheroidization areachieved; no separate or distinct processing steps are needed to achievedehydrogenation and spheroidization. After exiting the plasma, theproducts cool and solidify, locking in the spherical shape and are thencollected (265).

FIG. 3 is a flow chart illustrating another exemplary method (300) forproducing spherical powders, according to another embodiment of thepresent disclosure. In this example, the method (300) begins byintroducing a substantially continuous volume of filtered metal hydridefeed materials into a plasma torch. As discussed above, the plasma torchcan be a microwave generated plasma or an RF plasma torch (310). In oneexample embodiment, an AT-1200 rotating powder feeder (available fromThermach Inc.) allows a good control of the feed rate of the powder. Inan alternative embodiment, the powder can be fed into the plasma usingother suitable means, such as a fluidized bed feeder. The feed materialsmay be introduced at a constant rate, and the rate may be adjusted suchthat particles do not agglomerate during subsequent processing steps. Inanother exemplary embodiment, the feed materials to be processed arefirst sifted and classified according to their diameters, with a minimumdiameter of 1 micrometers (μm) and a maximum diameter of 22 μm, or aminimum of 22 μm and a maximum of 44 μm, or a minimum of 44 μm and amaximum of 70 μm, or a minimum of 70 μm and a maximum of 106 μm, or aminimum of 106 μm and a maximum of 300 μm. As will be appreciated, theseupper and lower values are provided for illustrative purposes only, andalternative size distribution values may be used in other embodiments.This eliminates recirculation of light particles above the hot zone ofthe plasma and also ensures that the process energy present in theplasma is sufficient to melt the particles without vaporization.Pre-screening allows efficient allocation of microwave power necessaryto melt the particles without vaporizing material.

Once introduced into the microwave plasma torch, the feed materials canbe entrained within an axis-symmetric laminar and/or turbulent flowtoward a microwave or RF generated plasma (320). In exemplaryembodiments, each particle within the process is entrained within aninert gas, such as argon. In some embodiments, the metal hydridematerials are exposed to a partial vacuum within the plasma (330).

Within the plasma, the feed materials are exposed to a substantiallyuniform temperature profile and are melted (340). In one example, thefeed materials are exposed to a uniform temperature profile ofapproximately between 4,000 and 8,000 K within the plasma. Melting thefeed materials within the plasma brings hydrogen to the surface of theliquid metal hydride where it can leave the particle, thus rapidlydehydrogenating the particles (350). The H₂ acts as a reducing agent,which may simultaneously deoxidize the metal. Surface tension of theliquid metal shapes each particle into a spherical geometry (360). Thus,dehydrogenated and spherical liquid metal particles are produced, whichcool and solidify into dehydrogenated and spherical metal powderproducts upon exiting the plasma (370). These particles can then becollected into bins (380). In some embodiments, the environment and/orsealing requirements of the bins are carefully controlled. That is, toprevent contamination or potential oxidation of the powders, theenvironment and or seals of the bins are tailored to the application. Inone embodiment, the bins are under a vacuum. In one embodiment, the binsare hermetically sealed after being filled with powder generated inaccordance with the present technology. In one embodiment, the bins areback filled with an inert gas, such as, for example argon. Because ofthe continuous nature of the process, once a bin is filled, it can beremoved and replaced with an empty bin as needed without stopping theplasma process.

The methods and processes in accordance with the invention (e.g., 200,250, 300) can be used to make spherical metal powders or spherical metalalloy powders. For example, if the starting feed material is a titaniumhydride material, the resulting powder will be a spherical titaniumpowder. If the starting feed material is a titanium alloy hydridematerial, the resulting powder will be a spherical titanium alloypowder. In one embodiment that features the use of a starting titaniumalloy hydride material, the resulting spherical titanium alloy powdercomprises spherioidized particles of Ti Al6-V4, with between 4% to 7%weight aluminum (e.g., 5.5 to 6.5% Al) and 3% to 5% weight vanadium(e.g., 3.5 to 4.5% vanadium).

FIG. 4 illustrates an exemplary microwave plasma torch that can be usedin the production of spheroidal and dehydrogenated metal or metal alloypowders, according to embodiments of the present disclosure. Asdiscussed above, metal hydride feed materials 9, 10 can be introducedinto a microwave plasma torch 3, which sustains a microwave generatedplasma 11. In one example embodiment, an entrainment gas flow and asheath flow (downward arrows) may be injected through inlets 5 to createflow conditions within the plasma torch prior to ignition of the plasma11 via microwave radiation source 1. In some embodiments, theentrainment flow and sheath flow are both axis-symmetric and laminar,while in other embodiments the gas flows are swirling. The feedmaterials 9 are introduced axially into the microwave plasma torch,where they are entrained by a gas flow that directs the materials towardthe plasma. As discussed above, the gas flows can consist of a noble gascolumn of the periodic table, such as helium, neon, argon, etc. Withinthe microwave generated plasma, the feed materials are melted, asdiscussed above, in order to dehydrogenate and spheroidize thematerials. Inlets 5 can be used to introduce process gases to entrainand accelerate particles 9, 10 along axis 12 towards plasma 11. First,particles 9 are accelerated by entrainment using a core laminar gas flow(upper set of arrows) created through an annular gap within the plasmatorch. A second laminar flow (lower set of arrows) can be createdthrough a second annular gap to provide laminar sheathing for the insidewall of dielectric torch 3 to protect it from melting due to heatradiation from plasma 11. In exemplary embodiments, the laminar flowsdirect particles 9, 10 toward the plasma 11 along a path as close aspossible to axis 12, exposing them to a substantially uniformtemperature within the plasma. In some embodiments, suitable flowconditions are present to keep particles 10 from reaching the inner wallof the plasma torch 3 where plasma attachment could take place.Particles 9, 10 are guided by the gas flows towards microwave plasma 11were each undergoes homogeneous thermal treatment. Various parameters ofthe microwave generated plasma, as well as particle parameters, may beadjusted in order to achieve desired results. These parameters mayinclude microwave power, feed material size, feed material insertionrate, gas flow rates, plasma temperature, residence time and coolingrates. In some embodiments, the cooling or quenching rate is not lessthan 10⁺³ degrees C./sec upon exiting plasma 11. As discussed above, inthis particular embodiment, the gas flows are laminar; however, inalternative embodiments, swirl flows or turbulent flows may be used todirect the feed materials toward the plasma.

FIG. 5 illustrates an exemplary method (500) of producing spheroidizedtitanium particles with a tailored or desired microstructure. Method 500includes several processing steps to treat metallic feed materials suchas, for example, titanium feed materials (e.g., titanium or titaniumalloys) to create spheroidized metallic particles with a desiredmicrostructure. In step 510, metallic (e.g., titanium based) feedmaterials comprising particles are feed into a plasma torch. Theparticles can be produced from crushing, pulverizing, or milling feedstock materials. In general, the feed stock particles have an averageparticle size of between 1 micron and 300 microns. In step 515, the feedstock particles are exposed to a microwave generated plasma to melt atleast the surface portion of the particles. The melted portions of theparticles allow for spheriodization of the particles. In step 520, thespheroidized particles are exposed to an inert gas such helium,nitrogen, argon or combinations/mixtures thereof. In step 525, thecooling processing variables/conditions are set and maintained toachieve a desired microstructure. For example, in embodiments in which amartensitic microstructure is desired throughout the entire particle,the cooling processing conditions are set for rapid cooling. As aresult, the residence time of the particles in the hot zone is selectedto allow for melting of the entire feedstock particle, the cooling gasflow rate is set to a fastest rate, and the amount of helium forming thecomposition of the cooling gas is set to a maximum available. Afterexposing the spheroidized particles to the selected cooling conditions,the spherical powders are collected in step 530.

FIG. 6 illustrates an exemplary method (600) of modifying metallic feedstock material to have a spheroidized shape and a desiredmicrostructure. The method of 600 includes several processing steps totreat metallic feed materials such as, for example, titanium feedmaterials (e.g., titanium or titanium alloys) to create spheroidizedmetallic particles with a desired microstructure. In this method,knowledge of the chemical composition of the feed stock (e.g., 99.9%pure titanium, Ti-6Al-4V, etc.) is used in combination with control overthermal processing conditions to achieve spheroidal particles with adesired microstructure different than the metallic feed stock material.In step 610, the composition of the Ti-based feed stock material isselected or analyzed to determine its composition. In step 615, adesired microstructure of a final product is determined. For example, itmay be determined that an α-phase 99% pure Ti equiaxed microstructurethroughout the spheroidized particle is desired. As a result, a slowerrate of cooling will be required than that used to produce a martensiticmicrostructure. Cooling processing parameters will be selected (step620), such as cooling gas flow rate, residence time, and/or compositionof cooling gas to achieve such a microstructure based upon thecomposition of the feed stock materials. In general, the microstructureof the final product will differ from the original feed stock material.That is an advantage of the present method is to be able to efficientlyprocess feed materials to create spheroidized particles with a desiredmicrostructure. After selecting or determining the cooling parameters,the feed stock particles are melted in the microwave generated plasma tospheriodize the particles in step 625. The spheroidized particles areexposed to an inert gas (step 630) and the determined or selectedcooling parameters are applied to form the desired microstructure.

The desired microstructure of the spheroidized particle (end product)can be tailored to meet the demands and material characteristics of itsuse. For example, the desired microstructure may be one that providesimproved ductility (generally associated with the α-phase). In anotherexample, the desired microstructure may be associated with the inclusionof α+β phase or regions of a with islands of β phase or vice-versa.Without wishing to be bound by theory, it is believe that the methods ofthe present disclosure allow for control over the phase of thespheroidized particles as the microwave generated plasma has a uniformtemperature profile, fine control over the hot zone, and the ability toselect and adjust cooling processing parameters.

Using the methods of the present technology, various microstructures,crystal structures and regions of differing microstructure and/orcrystal structures can be produced. Accordingly, new spheroidal titaniumparticles can be produced efficiently. For example, due to the abilitiesto control the hot zone and cooling processing parameters, the presenttechnology allows an operator to create multiple regions within thespheroidal particle. FIG. 7 shows such an embodiment. This figuresillustrates a spheroidal particle which has two distinct regions. Theouter or shell region 715 and an inner core 710. The original titaniumfeed material for this particle was a pure titanium α-phase powder. Thefeed material was exposed to the plasma under conditions (temperature,residence time, etc.) such that only a surface portion of the particlemelted, so that spheriodization could occur. Cooling rates appliedallowed for the transformation of the shell region to transform toβ-phase, leaving the core to retain the α-phase.

In another embodiment, not shown, the entire feed stock particle can bemelted and cooling parameters can be selected and applied to create acrystal structure that has the same phase as the feed stock material(e.g., retains α-phase) or is transformed to a new phase or mixture ofphases. Similarly, cooling processing parameters can be selected andapplied to create spheroidal particles that have the same microstructurethroughout the particle or various microstructures in two or moreregions (e.g., shell region, core region).

In describing exemplary embodiments, specific terminology is used forthe sake of clarity and in some cases reference to a figure. Forpurposes of description, each specific term is intended to at leastinclude all technical and functional equivalents that operate in asimilar manner to accomplish a similar purpose. Additionally, in someinstances where a particular exemplary embodiment includes a pluralityof system elements, device components or method steps, those elements,components or steps may be replaced with a single element, component orstep. Likewise, a single element, component or step may be replaced witha plurality of elements, components or steps that serve the samepurpose. Moreover, while exemplary embodiments have been shown anddescribed with references to particular embodiments thereof, those ofordinary skill in the art will understand that various substitutions andalterations in form and detail may be made therein without departingfrom the scope of the invention. Further still, other functions andadvantages are also within the scope of the invention.

1. A method of modifying at least one of particle shape ormicrostructure of a titanium based feedstock, the method comprising:melting at least a surface portion of particles of the titanium basedfeedstock in a plasma to spheroidize the particles; and setting andapplying cooling processing parameters to create spheroidized particleswith a microstructure, wherein the cooling process parameters compriseone or more of a cooling gas flow rate, a residence time of the titaniumbased feedstock, and a cooling gas composition, and wherein the titaniumbased feedstock has a α-phase crystal structure and the spheroidizedparticles includes one or more regions of a β-phase crystal structure.2. The method of claim 1, wherein the particles of the titanium basedfeedstock have a particle size of no less than 1.0 micrometers and nomore than 300 micrometers.
 3. The method of claim 1, wherein setting andapplying the cooling processing parameters comprises controlling acooling gas flow rate.
 4. The method of claim 1, wherein setting andapplying the selected cooling processing parameters comprisescontrolling a cooling gas composition.
 5. The method of claim 1, whereinthe cooling processing parameters are selected to create a martensiticmicrostructure in the spheroidized particles.
 6. The method of claim 1,wherein the cooling processing parameters are selected to create aWidmanstätten microstructure in the spheroidized particles.
 7. Themethod of claim 1, wherein the cooling processing parameters areselected to create an equiaxed microstructure in the spheroidizedparticles.
 8. The method of claim 1, wherein the cooling processingparameters are selected to create at least two regions in thespheroidized particles, each region having a different microstructure orcrystal structure.
 9. The method of claim 8, wherein the at least tworegions include a core portion and a skin portion.
 10. The method ofclaim 9, wherein the skin portion has a microstructure that is differentfrom the microstructure of the titanium based feedstock.
 11. A method ofmodifying at least one of particle shape or microstructure of a titaniumbased feedstock, the method comprising: melting at least a surfaceportion of particles of the titanium based feedstock in a plasma tospheroidize the particles; and setting and applying cooling processingparameters to create spheroidized particles with a microstructure,wherein the cooling process parameters comprise one or more of a coolinggas flow rate, a residence time of the titanium based feedstock, and acooling gas composition, and wherein the titanium based feedstock has asingle phase structure and the spheroidized particles have a multiphasestructure.
 12. The method of claim 11, wherein the particles of thetitanium based feedstock have a particle size of no less than 1.0micrometers and no more than 300 micrometers.
 13. The method of claim11, wherein setting and applying the selected cooling processingparameters comprises controlling a cooling gas flow rate.
 14. The methodof claim 11, wherein setting and applying the selected coolingprocessing parameters comprises controlling a cooling gas composition.15. The method of claim 11, wherein the cooling processing parametersare selected to create a martensitic microstructure in the spheroidizedparticles.
 16. The method of claim 11, wherein the cooling processingparameters are selected to create a Widmanstätten microstructure in thespheroidized particles.
 17. The method of claim 11, wherein the coolingprocessing parameters are selected to create an equiaxed microstructurein the spheroidized particles.
 18. The method of claim 11, wherein thecooling processing parameters are selected to create at least tworegions in the spheroidized particles, each region having a differentmicrostructure or crystal structure.
 19. The method of claim 18, whereinthe at least two regions include a core portion and a skin portion. 20.The method of claim 18, wherein the skin portion has a microstructurethat is different from the microstructure of the titanium basedfeedstock.